U.S. patent number 8,871,967 [Application Number 13/501,052] was granted by the patent office on 2014-10-28 for esters as perfuming ingredients.
This patent grant is currently assigned to Firmenich SA. The grantee listed for this patent is Peter Fankhauser, Umberto Maddalena. Invention is credited to Peter Fankhauser, Umberto Maddalena.
United States Patent |
8,871,967 |
Fankhauser , et al. |
October 28, 2014 |
Esters as perfuming ingredients
Abstract
The present invention relates to some perfuming ingredients
which are esters of formula (I) wherein R.sup.1 and R.sup.2
represent each a hydrogen atom or a methyl or ethyl group; and
R.sup.3 represents a C.sub.5-C.sub.8 group of formula satured or
unsatured linear, branched or cyclic group. ##STR00001##
Inventors: |
Fankhauser; Peter (Geneva,
CH), Maddalena; Umberto (Geneva, CH) |
Applicant: |
Name |
City |
State |
Country |
Type |
Fankhauser; Peter
Maddalena; Umberto |
Geneva
Geneva |
N/A
N/A |
CH
CH |
|
|
Assignee: |
Firmenich SA (Geneva,
CH)
|
Family
ID: |
41565892 |
Appl.
No.: |
13/501,052 |
Filed: |
October 15, 2010 |
PCT
Filed: |
October 15, 2010 |
PCT No.: |
PCT/IB2010/054673 |
371(c)(1),(2),(4) Date: |
April 09, 2012 |
PCT
Pub. No.: |
WO2011/055251 |
PCT
Pub. Date: |
May 12, 2011 |
Prior Publication Data
|
|
|
|
Document
Identifier |
Publication Date |
|
US 20120195844 A1 |
Aug 2, 2012 |
|
Foreign Application Priority Data
|
|
|
|
|
Nov 4, 2009 [EP] |
|
|
09174999 |
|
Current U.S.
Class: |
560/124; 560/123;
512/22; 424/65; 512/8 |
Current CPC
Class: |
C07C
69/533 (20130101); C07C 69/608 (20130101); C11B
9/003 (20130101); C11B 9/0034 (20130101); C07C
69/24 (20130101); C07C 2601/04 (20170501); C07C
2601/02 (20170501); C07C 2601/14 (20170501) |
Current International
Class: |
C07C
69/74 (20060101) |
Field of
Search: |
;560/123,124 ;512/8,22
;424/65 |
References Cited
[Referenced By]
U.S. Patent Documents
Other References
International Search and Written Opinion of the International
Searching Authority, application No. PCT/2010/054673, dated Jan.
12, 2011. cited by applicant .
Henrick et al., "Ovicidal Activity and Its Relation to Chemical
Structure for the Two Spotted Spider Mite (Tetranychus urticae
Koch) in a New Class of Miticides Containing the Cyclopropyl
Group," J. Agric. Food Chem., 24 (5): 1023-1029 (1976). cited by
applicant .
Le Baut et al., "Acides polyeniques. Activites antifongique et
bacteriostatique de derives de l'acide hexadiene-2,4 oique," Eur.
J. Med. Chem.--Chim. Ther., 18(5):441-445 (1983) (English
abstract). cited by applicant .
Sakauchi et al., "Syntheses and Odor Descriptions of
Cyclopropanated Compounds. Analogs of Aliphatic Monoterpene Dienols
and Non-branched Alcohols," Chemistry & Biodiversity, 3:544-552
(2006). cited by applicant.
|
Primary Examiner: Katakam; Sudhakar
Attorney, Agent or Firm: Winston & Strawn LLP
Claims
What is claimed is:
1. A compound of formula ##STR00025## in the form of any one of its
stereoisomers or of a mixture thereof, and wherein n is 0 or 1;
R.sup.l represents a hydrogen atom or a methyl or ethyl group;
R.sup.2 represents a hydrogen atom or a methyl or ethyl group; and
R.sup.3 represents: a) a C.sub.5-C.sub.8 group of formula
##STR00026## wherein one dotted line represents a carbon-carbon
single or double bond and the other a carbon-carbon single bond;
R.sup.4 represents a C.sub.1-4 alkyl or alkenyl group; R.sup.5'
represents a hydrogen atom or a methyl group; and each R.sup.5,
taken separately, represents a hydrogen atom or a methyl group, or
two R.sup.5, taken together, represent a CH.sub.2 group (in such a
case clearly both dotted lines represent a single bond); or R.sup.4
and one R.sup.5, taken together, represent a C.sub.3-4 hydrocarbon
group; or b) a C.sub.5-C.sub.8 group of formula ##STR00027##
wherein R.sup.6 represents a C.sub.3-4 alkyl or alkenyl group,
R.sup.6' represents a hydrogen atom or a methyl or ethyl group, and
R.sup.5 is defined as above; provided that cyclopropylmethyl
2,4-hexadienoate, cyclopropylmethyl hexanoate and cyclopropylmethyl
octanoate are excluded.
2. The compound according to claim 1, wherein R.sup.6' represents a
hydrogen atom.
3. The compound according to claim 1, wherein R.sup.3 represents:
a.sup.i) a C.sub.5-C.sub.7 group of formula ##STR00028## wherein
one dotted line represents a carbon-carbon double bond and the
other a carbon-carbon single bond; R.sup.4 represents a C.sub.1-3
alkyl or alkenyl group, preferably alkyl; R.sup.5 and R.sup.5'
represent each a hydrogen atom or a methyl group; and R.sup.5'',
taken alone, represents a hydrogen atom or taken together with
R.sup.5 represents a CH.sub.2 group (in such a case clearly both
dotted lines represent a single bond); a.sup.ii) a C.sub.5-C.sub.7
group of formula ##STR00029## R.sup.4 represents a C.sub.1-3 alkyl
or alkenyl group, preferably alkyl; R.sup.5' represents a hydrogen
atom or a methyl group; a.sup.iii) a C.sub.6-C.sub.8 group of
formula CH.sub.2(CH.sub.2).sub.mR.sup.7, wherein m represents 0 or
1 and R.sup.7 represents a C.sub.5-6 cyclic alkyl or alkenyl group;
or b.sup.i) a C.sub.5-C.sub.7 group of formula ##STR00030## wherein
R.sup.5 represents a hydrogen atom or a methyl group and R.sup.6
represents a C.sub.3 alkyl or alkenyl group.
4. The compound according to claim 1, wherein said compound is of
formula ##STR00031## in the form of any one of its stereoisomers or
of a mixture thereof, and wherein n is 0 or 1; R.sup.10 represents
a hydrogen atom or a methyl group; R.sup.8 represents a hydrogen
atom or a methyl group; and R.sup.9 represents a C.sub.4-6 linear
alkyl, alkenyl or alkadienyl group or a 2-R.sup.11-cycloprop-1-yl
group, R.sup.1l representing a methyl, ethyl or propyl group.
5. A compound selected from the group consisting of
cyclopropylmethyl (3Z)-3-hexenoate, (E)-cyclopropylmethyl
hex-4-enoate or (Z)-cyclobutylmethyl hex-3-enoate,
(E)-cyclopropylmethyl hex-2-enoate, cyclopropylmethyl
2-methylhexanoate, (Z)-1-cyclopropylethyl 3-hexenoate,
cyclopropylmethyl 3-cyclohexylpropanoate, (E)-1-cyclopropylethyl
2-methylhex-2-enoate, cyclopropylmethyl (3E)-3-hexenoate,
(Z)-cyclobutylmethyl hex-3-enoate, (Z)-cyclopropylmethyl
3-methylhept-2-enoate and (E)-cyclopropylmethyl
3-methylhept-2-enoate.
6. The compound according to claim 5, which is cyclopropylmethyl
(3Z)-3-hexenoate, or (E)-cyclopropylmethyl hex-4-enoate or
(Z)-cyclobutylmethyl hex-3-enoate.
7. A method to confer, enhance, improve or modify the odor
properties of a perfuming composition or of a perfumed article,
which method comprises adding to said composition or article an
effective amount of at least a compound of formula ##STR00032## in
the form of any one of its stereoisomers or of a mixture thereof,
and wherein n is 0 or 1; R.sup.l represents a hydrogen atom or a
methyl or ethyl group; R.sup.2 represents a hydrogen atom or a
methyl or ethyl group; and R.sup.3 represents: a) a C.sub.5-C.sub.8
group of formula ##STR00033## wherein one dotted line represents a
carbon-carbon single or double bond and the other a carbon-carbon
single bond; R.sup.4 represents a C.sub.1-4 alkyl or alkenyl group;
R.sup.5' represents a hydrogen atom or a methyl group; and each
R.sup.5, taken separately, represents a hydrogen atom or a methyl
group, or two R.sup.5, taken together, represent a CH.sub.2 group
(in such a case clearly both dotted lines represent a single bond);
or R.sup.4 and one R.sup.5, taken together, represent a C.sub.3-4
hydrocarbon group; or b) a C.sub.5-C.sub.8 group of formula
##STR00034## wherein R.sup.6 represents a C.sub.3-4 alkyl or
alkenyl group, R.sup.6' represents a hydrogen atom or a methyl or
ethyl group, and R.sup.5 is defined as above.
8. The method according to claim 7, wherein said compound is
cyclopropylmethyl (3Z)-3-hexenoate, (E)-cyclopropylmethyl
hex-4-enoate or (Z)-cyclobutylmethyl hex-3-enoate,
(E)-cyclopropylmethyl hex-2-enoate, cyclopropylmethyl
2-methylhexanoate, (Z)-1-cyclopropylethyl 3-hexenoate,
cyclopropylmethyl 3-cyclohexylpropanoate, (E)-1-cyclopropylethyl
2-methylhex-2-enoate, cyclopropylmethyl (3E)-3-hexenoate,
(Z)-cyclobutylmethyl hex-3-enoate, (Z)-(1-methylcyclopropyl)methyl
hex-3-enoate, (Z)-cyclopropylmethyl 3-methylhept-2-enoate or
(E)-cyclopropylmethyl 3-methylhept-2-enoate.
9. The method according to claim 7, which is cyclopropylmethyl
(3Z)-3-hexenoate, or (E)-cyclopropylmethyl hex-4-enoate or
(Z)-cyclobutylmethyl hex-3-enoate.
10. A perfuming ingredient in the form of a composition comprising
i) at least one compound of formula (I), as defined in claim 1; ii)
at least one ingredient selected from the group consisting of a
perfumery carrier and a perfumery base; and iii) optionally at
least one perfumery adjuvant.
11. The perfuming ingredient according to claim 10, wherein the
compound is selected from the group consisting of cyclopropylmethyl
(3Z)-3-hexenoate, (E)-cyclopropylmethyl hex-4-enoate or
(Z)-cyclobutylmethyl hex-3-enoate, (E)-cyclopropylmethyl
hex-2-enoate, cyclopropylmethyl 2-methylhexanoate,
(Z)-1-cyclopropylethyl 3-hexenoate, cyclopropylmethyl
3-cyclohexylpropanoate, (E)-1-cyclopropylethyl
2-methylhex-2-enoate, cyclopropylmethyl (3E)-3-hexenoate,
(Z)-cyclobutylmethyl hex-3-enoate, (Z)-cyclopropylmethyl
3-methylhept-2-enoate and (E)-cyclopropylmethyl
3-methylhept-2-enoate.
12. The perfuming ingredient according to claim 10, which is
cyclopropylmethyl (3Z)-3-hexenoate, or (E)-cyclopropylmethyl
hex-4-enoate or (Z)-cyclobutylmethyl hex-3-enoate.
13. A perfuming consumer product: i) as perfuming ingredient, at
least one compound of formula (I), as defined in claim 1; and ii) a
perfumery consumer base.
14. The consumer product according to claim 13, wherein the
compound is selected from the group consisting of cyclopropylmethyl
(3Z)-3-hexenoate, (E)-cyclopropylmethyl hex-4-enoate or
(Z)-cyclobutylmethyl hex-3-enoate, (E)-cyclopropylmethyl
hex-2-enoate, cyclopropylmethyl 2-methylhexanoate,
(Z)-1-cyclopropylethyl 3-hexenoate, cyclopropylmethyl
3-cyclohexylpropanoate, (E)-1-cyclopropylethyl
2-methylhex-2-enoate, cyclopropylmethyl (3E)-3-hexenoate,
(Z)-cyclobutylmethyl hex-3-enoate, (Z)-cyclopropylmethyl
3-methylhept-2-enoate and (E)-cyclopropylmethyl
3-methylhept-2-enoate.
15. The consumer product according to claim 13, which is
cyclopropylmethyl (3Z)-3-hexenoate, or (E)-cyclopropylmethyl
hex-4-enoate or (Z)-cyclobutylmethyl hex-3-enoate.
16. The consumer product according to claim 13, wherein the
perfumery consumer base is a perfume, a fabric care product, a
body-care product, an air care product or a home care product.
17. The consumer product according to claim 13, wherein the
perfumery consumer base is a fine perfume, a cologne, an
after-shave lotion, a liquid or solid detergent, a fabric softener,
a fabric refresher, an ironing water, a paper, a bleach, a shampoo,
a coloring preparation, a hair spray, a vanishing cream, a
deodorant or antiperspirant, a perfumed soap, shower or bath
mousse, oil or gel, a hygiene product, an air freshener, a "ready
to use" powdered air freshener, a wipe, a dish detergent or
hard-surface detergent.
Description
This application is a 371 of International Patent Application
PCT/IB2010/054673, filed Oct. 15, 2010.
TECHNICAL FIELD
The present invention relates to the field of perfumery. More
particularly, it concerns some esters of cyclopropylmethanol or
cyclobutylmethanol and their methyl substituted derivatives as
defined herein below. The present invention concerns the use of
said compounds in the perfumery industry as well as the
compositions or articles containing said compounds.
PRIOR ART
To the best of our knowledge, only three compounds of formula (I)
are reported in the prior art. Said compounds are cyclopropylmethyl
2,4-hexadienoate, mentioned in Eur. J. Med. Chem., 1983, 18, 441 as
a chemical compound in a study for antifungal activity, and
cyclopropylmethyl hexanoate and cyclopropylmethyl octanoate,
mentioned in J. Agric. Food Chem., 1976, 24, 1023 as a chemical
compound in a study for miticides activity.
However, these prior art documents do not report or suggest any
organoleptic properties of the compounds of formula (I), or any use
of said compounds in the field of perfumery.
One may also cite some analogues of the present invention's
compounds which are described as having interesting perfuming
properties. These compounds are reported in Chemistry and
Biodiversity, 2006, pg 544. These documents report three esters of
cyclopropylmethanol derivatives (i.e. compounds 9a
([2-ethylcyclopropyl)methyl benzoate], 10a
([2-ethylcyclopropyl)methyl acetate]) and
11a([2-ethylcyclopropyl)methyl butyrate])) which all have a
different chemical structure and very different odors (specifically
mentioned no green notes). This prior art document does not report
or suggest or anticipate any organoleptic properties of the
compounds of formula (I), or any use of said compounds in the field
of perfumery.
DESCRIPTION OF THE INVENTION
We have now surprisingly discovered that a compound of formula
##STR00002## in the form of any one of its stereoisomers or of a
mixture thereof, and wherein n is 0 or 1, R.sup.1 represents a
hydrogen atom or a methyl or ethyl group; R.sup.2 represents a
hydrogen atom or a methyl or ethyl group; and R.sup.3
represents:
a) a C.sub.5-C.sub.8 group of formula
##STR00003## wherein one dotted line represents a carbon-carbon
single or double bond and the other a carbon-carbon single bond;
R.sup.4 represents a C.sub.1-4 alkyl or alkenyl group; R.sup.5'
represents a hydrogen atom or a methyl group; and each R.sup.5,
taken separately, represents a hydrogen atom or a methyl group, or
two R.sup.5, taken together, represent a CH.sub.2 group (in such a
case clearly both dotted lines represent a single bond); or R.sup.4
and one R.sup.5, taken together, represent a C.sub.3-4 hydrocarbon
group; or
b) a C.sub.5-C.sub.8 group of formula
##STR00004## wherein R.sup.6 represents a C.sub.3-4 alkyl or
alkenyl group, R.sup.6' represents a hydrogen atom or a methyl or
ethyl group, and R.sup.5 is defined as above; can be used as
perfuming ingredient, for instance to impart an odor characterized
by a combination of a green note with fruity and/or alliaceous
characters or aspects.
For the sake of clarity, by the expression "wherein one dotted line
represents a carbon-carbon single or double bond and the other a
carbon-carbon single bond", or the similar, it is meant the normal
meaning understood by a person skilled in the art, i.e. that the
whole bonding (solid and dotted line) between the carbon atoms
connected by said dotted line, e.g. carbon 2 and 3, is a
carbon-carbon single or double bond.
According to a particular embodiment of the invention, R.sup.6'
represents a hydrogen atom or a methyl or ethyl group.
Alternatively, R.sup.6' represents a hydrogen atom.
According to any one of the above embodiments of the invention,
R.sup.1 and R.sup.2 represent each a hydrogen atom or a methyl
group. Alternatively, R.sup.1 and R.sup.2 represent each a hydrogen
atom.
According to any one of the above embodiments of the invention,
said compounds (I) are those wherein R.sup.3 represents: a.sup.i) a
C.sub.5-C.sub.7 group of formula
##STR00005## wherein one dotted line represents a carbon-carbon
double bond and the other a carbon-carbon single bond; R.sup.4
represents a C.sub.1-3 alkyl or alkenyl group, preferably alkyl;
R.sup.5 and R.sup.5' represent each a hydrogen atom or a methyl
group; and R.sup.5'', taken alone, represents a hydrogen atom or
taken together with R.sup.5 represents a CH.sub.2 group (in such a
case clearly both dotted lines represent a single bond); a.sup.ii)
a C.sub.5-C.sub.7 group of formula
##STR00006## R.sup.4 represents a C.sub.1-3 alkyl or alkenyl group,
preferably alkyl; R.sup.5' represents a hydrogen atom or a methyl
group; a.sup.iii) a C.sub.6-C.sub.8 group of formula
CH.sub.2(CH.sub.2).sub.mR.sup.7, wherein m represents 0 or 1 and
R.sup.7 represents a C.sub.5-6 cyclic alkyl or alkenyl group; or
b.sup.i) a C.sub.5-C.sub.7 group of formula
##STR00007## wherein R.sup.5 represents a hydrogen atom or a methyl
group and R.sup.6 represents a C.sub.3 alkyl or alkenyl group.
According to a particular embodiment, said invention's compounds
are those wherein R.sup.3 represents a group as defined under a),
said compounds having a green note with a fruity character.
According to a particular embodiment of the invention, said
compounds (I) are to those of formula (I) wherein R.sup.3
represents a group as defined under a.sup.i) or b.sup.i).
According to a particular embodiment of the invention, said
compounds (I) are those of formula
##STR00008## in the form of any one of its stereoisomers or of a
mixture thereof, and wherein n is 0 or 1; R.sup.10 represents a
hydrogen atom or a methyl group; R.sup.8 represents a hydrogen atom
or a methyl group; and R.sup.9 represents a C.sub.4-6 linear alkyl,
alkenyl or alkadienyl group or a 2-R.sup.11-cycloprop-1-yl group,
R.sup.11 representing a methyl, ethyl or propyl group.
According to a particular embodiment of the invention, said
compounds (II) are those wherein R.sup.10 represents a hydrogen
atom.
According to a particular embodiment of the invention, said
compounds (II) are those wherein n is 0.
According to any one of the above embodiments of said compounds
(II), said compounds are those wherein R.sup.9 represents a
C.sub.4-5 linear alkyl or alkenyl group or a
2-R.sup.11-cycloprop-1-yl group, R.sup.11 representing a methyl or
ethyl group.
Alternatively, R.sup.9 represents a C.sub.4 or C.sub.5 linear
alkenyl group. Said compounds of formula (II) can be used as
perfuming ingredients, for instance to impart an odor characterized
by a combination of a green note with fruity and alliaceous
aspects.
According to any one of the above embodiments of the invention,
said compounds (I) or (II) are C.sub.10-C.sub.13 compounds.
Alternatively said invention's compounds are C.sub.10 or C.sub.11
compounds.
As mentioned above, the compounds of formula (I) possess very
interesting odors which allow to distinguish them from other
structurally related prior art perfuming ingredients. In particular
compounds (I) distinguish themselves by associating a strong green
note with a peculiar fruity, e.g. pear, character and often having
also a nice alliacous aspect. Said invention's compounds
distinguish them also by lacking a, or by not possessing a
significant, woody, citrusy or almond note.
As specific examples of the invention's compounds, one may cite, as
non-limiting example, cyclopropylmethyl (3Z)-3-hexenoate which
possesses a nice and very strong green note having a clear
fruity-pear character, as well as leafy and alliaceous aspects.
This compound distinguishes itself from the other generic green
notes, such as the cis-3-hexenol esters, by having a much stronger
and performing odor as well as its peculiar fruity-pear character
and its unique and natural alliacous aspect reminding of bear's
garlic.
As other example one may cite (E)-cyclopropylmethyl hex-4-enoate,
which possesses an odor similar to the one mentioned above but
distinguishing itself by having a hexanal note as well as being
less powerful than its analogue cyclopropylmethyl
(3Z)-3-hexenoate.
As other specific, but non-limiting, examples of the invention's
compounds, one may cite the following ones in Table 1.
TABLE-US-00001 TABLE 1 Invention's compounds and their odor
properties Compound structure and name Odor notes ##STR00009##
Green, fruity cyclopropylmethyl heptanoate ##STR00010## Green,
garlic, pepper, slightly fruity (E)-cyclopropylmethyl hex-2-enoate
##STR00011## Green, fruity and ylang cyclopidene cyclopropylmethyl
2-methylhexanoate ##STR00012## Green, fruity-pear, alliaceous
(Z)-1-cyclopropylethyl 3-hexenoate ##STR00013## Green, pear,
slightly alliaceous, violette (E)-cyclopropylmethyl
3-methylhex-2-enoate ##STR00014## Green with fruity aspect
cyclopropylmethyl octanoate ##STR00015## Green, fruity-apple,
sweety cyclopropylmethyl 3-cyclohexylpropanoate ##STR00016## Green,
sweet fruity, slightly alliaceous, onion cyclopropylmethyl
hexanoate ##STR00017## Green with fruity aspect
(E)-1-cyclopropylethyl 2-methylhex-2-enoate ##STR00018## Green,
fruity ##STR00019## cyclopropylmethyl 2-(2-ethylcyclopropyl)acetate
##STR00020## Green, pear, onion cyclopropylmethyl (3E)-3-hexenoate
##STR00021## Green, pear, slightly alliaceous (Z)-cyclobutylmethyl
hex-3-enoate ##STR00022## Green, pear ##STR00023## mixture of
(Z)-cyclopropylmethyl 3- methylhept-2-enoate and
(E)-cyclopropylmethyl 3-methylhept-2-enoate ##STR00024## Green,
pear, pine, alliaceous (Z)-(1-methylcyclopropyl)methyl
hex-3-enoate
According to a particular embodiment of the invention, the compound
of formula (I) is cyclopropylmethyl (3Z)-3-hexenoate,
(E)-cyclopropylmethyl hex-4-enoate or (Z)-cyclobutylmethyl
hex-3-enoate, (E)-cyclopropylmethyl hex-2-enoate, cyclopropylmethyl
2-methylhexanoate, (Z)-1-cyclopropylethyl 3-hexenoate,
cyclopropylmethyl 3-cyclohexylpropanoate, cyclopropylmethyl
hexanoate, (E)-1-cyclopropylethyl 2-methylhex-2-enoate,
cyclopropylmethyl (3E)-3-hexenoate, (Z)-cyclobutylmethyl
hex-3-enoate, (Z)-(1-methylcyclopropyl)methyl hex-3-enoate,
(Z)-cyclopropylmethyl 3-methylhept-2-enoate or
(E)-cyclopropylmethyl 3-methylhept-2-enoate.
According to a particular embodiment of the invention, the compound
of formula (I) is cyclopropylmethyl (3Z)-3-hexenoate, or
(E)-cyclopropylmethyl hex-4-enoate or (Z)-cyclobutylmethyl
hex-3-enoate.
As mentioned above, the invention concerns the use of a compound of
formula (I) as perfuming ingredient. In other words it concerns a
method to confer, enhance, improve or modify the odor properties of
a perfuming composition or of a perfumed article, which method
comprises adding to said composition or article an effective amount
of at least a compound of formula (I). By "use of a compound of
formula (I)" it has to be understood here also the use of any
composition containing compound (I) and which can be advantageously
employed in perfumery industry as active ingredients.
Said compositions, which in fact can be advantageously employed as
perfuming ingredient, are also an object of the present
invention.
Therefore, another object of the present invention is a perfuming
composition comprising: i) as perfuming ingredient, at least one
invention's compound as defined above; ii) at least one ingredient
selected from the group consisting of a perfumery carrier and a
perfumery base; and iii) optionally at least one perfumery
adjuvant.
By "perfumery carrier" we mean here a material which is practically
neutral from a perfumery point of view, i.e. that does not
significantly alter the organoleptic properties of perfuming
ingredients. Said carrier may be a liquid or a solid.
As liquid carrier one may cite, as non-limiting examples, an
emulsifying system, i.e. a solvent and a surfactant system, or a
solvent commonly used in perfumery. A detailed description of the
nature and type of solvents commonly used in perfumery cannot be
exhaustive. However, one can cite as non-limiting example solvents
such as dipropyleneglycol, diethyl phthalate, isopropyl myristate,
benzyl benzoate, 2-(2-ethoxyethoxy)-1-ethanol or ethyl citrate,
which are the most commonly used.
As solid carrier one may cite, as non-limiting examples, absorbing
gums or polymers, or yet encapsulating materials. Examples of such
materials may comprise wall-forming and plasticizing materials,
such as mono, di- or trisaccharides, natural or modified starches,
hydrocolloids, cellulose derivatives, polyvinyl acetates,
polyvinylalcohols, proteins or pectins, or yet the materials cited
in reference texts such as H. Scherz, Hydrokolloids:
Stabilisatoren, Dickungs- and Gehermittel in Lebensmittel, Band 2
der Schriftenreihe Lebensmittelchemie, Lebensmittelqualitat, Behr's
VerlagGmbH & Co., Hamburg, 1996. The encapsulation is a well
known process to a person skilled in the art, and may be performed,
for instance, using techniques such as spray-drying, agglomeration
or yet extrusion; or consists of a coating encapsulation, including
coacervation and complex coacervation techniques.
By "perfumery base" we mean here a composition comprising at least
one perfuming co-ingredient.
Said perfuming co-ingredient is not of the formula (I). Moreover,
by "perfuming co-ingredient" it is meant here a compound, which is
used in perfuming preparation or composition to impart a hedonic
effect. In other words such a co-ingredient, to be considered as
being a perfuming one, must be recognized by a person skilled in
the art as being able to impart or modify in a positive or pleasant
way the odor of a composition, and not just as having an odor.
The nature and type of the perfuming co-ingredients present in the
base do not warrant a more detailed description here, which in any
case would not be exhaustive, the skilled person being able to
select them on the basis of its general knowledge and according to
intended use or application and the desired organoleptic effect. In
general terms, these perfuming co-ingredients belong to chemical
classes as varied as alcohols, lactones, aldehydes, ketones,
esters, ethers, acetates, nitriles, terpenoids, nitrogenous or
sulphurous heterocyclic compounds and essential oils, and said
perfuming co-ingredients can be of natural or synthetic origin.
Many of these co-ingredients are in any case listed in reference
texts such as the book by S. Arctander, Perfume and Flavor
Chemicals, 1969, Montclair, N.J., USA, or its more recent versions,
or in other works of a similar nature, as well as in the abundant
patent literature in the field of perfumery. It is also understood
that said co-ingredients may also be compounds known to release in
a controlled manner various types of perfuming compounds.
For the compositions which comprise both a perfumery carrier and a
perfumery base, other suitable perfumery carriers, than those
previously specified, can be also ethanol, water/ethanol mixtures,
limonene or other terpenes, isoparaffins such as those known under
the trademark Isopar.RTM. (origin: Exxon Chemical) or glycol ethers
and glycol ether esters such as those known under the trademark
Dowanol.RTM. (origin: Dow Chemical Company).
By "perfumery adjuvant" we mean here an ingredient capable of
imparting additional added benefits such as a color, a particular
light resistance, chemical stability, etc. A detailed description
of the nature and type of adjuvant commonly used in perfuming bases
cannot be exhaustive, but it has to be mentioned that said
ingredients are well known to a person skilled in the art.
An invention's composition consisting of at least one compound of
formula (I) and at least one perfumery carrier represents a
particular embodiment of the invention as well as a perfuming
composition comprising at least one compound of formula (I), at
least one perfumery carrier, at least one perfumery base, and
optionally at least one perfumery adjuvant.
It is useful to mention here that the possibility to have, in the
compositions mentioned above, more than one compound of formula (I)
is important as it enables the perfumer to prepare accords,
perfumes, possessing the odor tonality of various compounds of the
invention, creating thus new tools for their work.
Preferably, any mixture resulting directly from a chemical
synthesis, e.g. without an adequate purification, in which the
compound of the invention would be involved as a starting,
intermediate or end-product could not be considered as a perfuming
composition according to the invention.
Furthermore, the invention's compound can also be advantageously
used in all the fields of modern perfumery, i.e. fine or functional
perfumery, to positively impart or modify the odor of a consumer
product into which said compound (I) is added. Consequently, a
perfuming consumer product which comprises: i) as perfuming
ingredient, at least one compound of formula (I), as defined above;
and ii) a perfumery consumer base; is also an object of the present
invention.
The invention's compound can be added as such or as part of an
invention's perfuming composition.
For the sake of clarity, it has to be mentioned that, by "perfuming
consumer product" it is meant a consumer product which is expected
to deliver at least a perfuming effect, in other words it is a
perfumed consumer product. For the sake of clarity, it has to be
mentioned that, by "perfumery consumer base" we mean here the
functional formulation, as well as optionally additional benefit
agents, corresponding to a consumer product which is compatible
with perfuming ingredients and is expected to deliver a pleasant
odor to the surface to which it is applied (e.g. skin, hair,
textile, or home surface). In other words, a perfuming consumer
product according to the invention comprises the functional
formulation, as well as optionally additional benefit agents,
corresponding to the desired consumer product, e.g. a detergent or
an air freshener, and an olfactive effective amount of at least one
invention's compound.
The nature and type of the constituents of the perfumery consumer
base do not warrant a more detailed description here, which in any
case would not be exhaustive, the skilled person being able to
select them on the basis of his general knowledge and according to
the nature and the desired effect of said product.
Non-limiting examples of suitable perfumery consumer bases can be a
perfume, such as a fine perfume, a cologne or an after-shave
lotion; a fabric care product, such as a liquid or solid detergent,
a fabric softener, a fabric refresher, an ironing water, a paper,
or a bleach; a body-care product, such as a hair care product (e.g.
a shampoo, a coloring preparation or a hair spray), a cosmetic
preparation (e.g. a vanishing cream or a deodorant or
antiperspirant), or a skin-care product (e.g. a perfumed soap,
shower or bath mousse, oil or gel, or a hygiene product); an air
care product, such as an air freshener or a "ready to use" powdered
air freshener; or a home care product, such as a wipe, a dish
detergent or hard-surface detergent.
Some of the above-mentioned consumer product bases may represent an
aggressive medium for the invention's compound, so that it may be
necessary to protect the latter from premature decomposition, for
example by encapsulation or by chemically bounding it to another
chemical which is suitable to release the invention's ingredient
upon a suitable external stimulus, such as an enzyme, light, heat
or a change of pH.
The proportions in which the compounds according to the invention
can be incorporated into the various aforementioned articles or
compositions vary within a wide range of values. These values are
dependent on the nature of the article to be perfumed and on the
desired organoleptic effect as well as the nature of the
co-ingredients in a given base when the compounds according to the
invention are mixed with perfuming co-ingredients, solvents or
additives commonly used in the art.
For example, in the case of perfuming compositions, typical
concentrations are in the order of 0.01% to 3% by weight, or even
more, of the compounds of the invention based on the weight of the
composition into which they are incorporated. Concentrations lower
than these, such as in the order of 0.001% to 2% by weight, can be
used when these compounds are incorporated into perfumed articles,
percentage being relative to the weight of the article.
The invention's compounds can be prepared according to a method
involving a trans esterification of an appropriate ester of the
acid R.sup.3COOH, e.g. a methyl or ethyl ester of R.sup.3COOH, with
an appropriate alcohol, such as cyclopropylmethanol. Alternatively
the compounds (I) can be obtained by a direct esterification of an
acid R.sup.3COOH with an appropriate alcohol. Typical examples are
provided herein below in the Examples section.
EXAMPLES
The invention will now be described in further detail by way of the
following examples, wherein the abbreviations have the usual
meaning in the art, the temperatures are indicated in degrees
centigrade (.degree. C.); the NMR spectral data were recorded in
CDCl.sub.3 (if not stated otherwise) with a 360 or 400 MHz machine
for .sup.1H and .sup.13C, the chemical shifts .delta. are indicated
in ppm with respect to TMS as standard, the coupling constants J
are expressed in Hz.
Example 1
Synthesis of Compounds of Formula (I)
General Procedures for Obtaining the Invention's Compounds
Ester Preparation--Method A
The carboxylic acid (69 mmol), the cycloaliphatic alcohol (62
mmol), p-toluenesulphonic acid hydrate (0.16 g; 0.84 mmol) and
n-heptane (30 g) were charged in a 100 ml round bottom flask and
heated to reflux. The water formed by the reaction was removed
using a Dean Stark trap. The reaction progress was monitored by GC.
After a few hours, having achieved full conversion, the reaction
mixture was cooled to room temperature, diluted with MTBE (30 ml)
and washed repeatedly with aq. sodium carbonate. Drying over anh.
sodium sulphate, filtration and removal of the solvent afforded the
crude ester in quantitative yield.
Distillation through a 15 cm Vigreux column or flash distillation
(bulb to bulb) under reduced pressure gave the pure ester.
Ester Preparation--Method B
The methyl carboxylate (116 mmol), the cycloaliphatic alcohol (234
mmol), dioctyl tin oxide (1.0 g; 2.8 mmol) and n-heptane (20 g)
were charged in a 100 ml round bottom flask and heated to reflux.
The methanol formed by the reaction was removed using a Dean Stark
trap. The reaction progress was monitored by GC. After 24 hours the
solvent was distilled off to yield the crude ester in quantitative
yield. Distillation through a 15 cm Vigreux column under reduced
pressure gave the pure ester.
Ester Preparation--Method C
The alkyl carboxylate (364 mmol), the cycloaliphatic alcohol (277
mmol) and dioctyl tin oxide (1.0 g; 2.8 mmol) were charged in the
distillation flask of a 35 cm Fischer Spaltrohr.RTM. column and
heated to 120-130.degree. C. Vacuum was applied, to continuously
distill the alkanol formed by transesterification. The reflux ratio
and distillation rate were adjusted in order to distill alkanol
containing only a minimum amount of the higher-boiling
cycloaliphatic alcohol. The reaction progress was monitored by GC.
As the reaction rate slowed down another portion of cycloaliphatic
alcohol (97 mmol) was added, to increase further the conversion of
the starting alkyl carboxylate. Finally the desired ester was
distilled under reduced pressure using the same apparatus.
Hydrogenation--General Method
The unsaturated ester (35 mmol), palladium on charcoal (5% Pd/C,
0.3 g) and ethyl acetate (30 ml) were charged in a 100 ml stirred
autoclave and hydrogenated (4 bar hydrogen) at 25.degree. C. for 24
hours. Filtration over Celite and removal of the solvent followed
by flash distillation (bulb to bulb) under vacuum afforded the
desired saturated ester.
Cyclopropanation--General Method
To an oven dried 1000 ml round bottomed flask was added methylene
chloride (500 ml) under an argon atmosphere. Diethylzinc (100 ml,
1M in hexanes; 100 mmol) was added, and then diiodomethane (57.0 g,
213 mmol) was introduced dropwise over 1.5 hours. Following
stirring for 30 minutes (a white precipitate formed) the
unsaturated ester (36 mmol) was added dropwise over 20 minutes and
the reaction was stirred over night at room temperature. The
reaction mixture was poured into a 20% aq. potassium carbonate
solution (500 ml) and then filtered through a pad of Celite in a
sintered funnel. The organic layer was separated and dried over
anh. sodium sulfate. Filtration of the drying agent, concentration
and flash distillation gave the crude cyclopropanated material.
This product, containing still some starting ester was subjected to
a second cyclopropanation procedure. Distillation through a 15 cm
Vigreux column under reduced pressure gave the pure cyclopropanated
ester.
Using the above general procedure were prepared the following
compounds:
(Z)-cyclopropylmethyl hex-3-enoate
Prepared from (Z)-methyl hex-3-enoate and cyclopropanemethanol
according to the ester preparation method B described above.
Alternatively prepared from (Z)-n-butyl hex-3-enoate and
cyclopropanemethanol according to the ester preparation method
C.
Bp.: 103.degree. C./13 mbar
.sup.13C-NMR: 3.2 (t), 9.8 (d), 13.9 (q), 20.8 (t), 32.9 (t), 69.4
(t), 120.4 (d), 135.0 (d), 172.2 (s);
.sup.1H-NMR: 0.26-0.30 (m, 2H); 0.54-0.59 (m, 2H); 0.99 (t, J=7.4,
3H); 1.07-1.18 (m, 1H); 2.03-2.10 (m, 2H); 3.11 (d, J=6.30, 2H);
3.92 (d, J=7.4, 2H); 5.50-5.60 (m, 2H).
(E)-cyclopropylmethyl hex-3-enoate
Prepared from (E)-methyl hex-3-enoate and cyclopropanemethanol
according to the ester preparation method B described above.
Bp.: 71.degree. C./4.5 mbar
.sup.13C-NMR: 3.2 (t), 9.8 (d), 13.5 (q), 25.5 (t), 38.1 (t), 69.3
(t), 120.7 (d), 136.2 (d), 172.4 (s);
.sup.1H-NMR: 0.26-0.30 (m, 2H); 0.54-0.59 (m, 2H); 0.99 (t, J=7.2,
3H); 1.07-1.18 (m, 1H); 2.02-2.09 (m, 2H); 3.04 (d, J=6.30, 2H);
3.91 (d, J=7.4, 2H); 5.50-5.65 (m, 2H).
(E)-cyclopropylmethyl hex-2-enoate
Prepared from (E)-methyl hex-2-enoate and cyclopropanemethanol
according to the ester preparation method B described above.
Bp.: 61.degree. C./1 mbar
.sup.13C-NMR: 3.2 (t), 9.9 (d), 13.7 (q), 21.3 (t), 34.2 (t), 69.0
(t), 121.4 (d), 149.3 (d), 166.9 (s);
.sup.1H-NMR: 0.27-0.31 (m, 2H); 0.55-0.60 (m, 2H); 0.94 (t, J=7.5,
3H); 1.10-1.20 (m, 1H); 1.45-1.54 (m, 2H); 2.16-2.21 (m, 2H); 3.96
(d, J=7.2, 2H); 5.85 (d, J=15.2; H); 6.94-7.02 (m, 1H).
Cyclopropylmethyl 3-methylhex-2-enoate
Prepared from methyl 3-methylhex-2-enoate and cyclopropanemethanol
according to the ester preparation method B described above. The Z
and E isomer were separated by distillation under vacuum using a 35
cm Fischer Spaltrohr.RTM. column.
Z-Isomer:
Bp.: 60.degree. C./2.5 mbar
.sup.13C-NMR: 3.2 (t), 9.9 (d), 14.1 (q), 21.5 (t), 25.2 (q), 35.3
(t), 68.3 (t), 116.3 (d), 160.5 (s), 166.5 (s);
.sup.1H-NMR: 0.25-0.30 (m, 2H); 0.53-0.58 (m, 2H); 0.95 (t, J=7.5,
3H); 1.09-1.19 (m, 1H); 1.46-1.56 (m, 2H); 1.88 (s, 3H); 2.61 (t,
2H); 3.91 (d, J=7.2, 2H); 5.70 (s, 1H).
E-Isomer:
Bp.: 75.degree. C./2.5 mbar
.sup.13C-NMR: 3.3 (t), 9.9 (d), 13.7 (q), 18.7 (q), 20.6 (t), 43.0
(t), 68.3 (t), 115.6 (d), 160.1 (s), 167.0 (s);
.sup.1H-NMR: 0.26-0.30 (m, 2H); 0.54-0.59 (m, 2H); 0.92 (t, J=7.5,
3H); 1.09-1.19 (m, 1H); 1.47-1.56 (m, 2H); 2.12 (t, 2H); 2.15 (s,
3H); 3.92 (d, J=7.2 Hz, 2H); 5.7 (s, 1H).
(Z)-1-cyclopropylethyl 3-hexenoate
Prepared from methyl (3Z)-3-hexenoate and cyclopropyl methyl
carbinol according to the ester preparation method B described
above.
Bp.: 68.degree. C./3.8 mbar
.sup.13C-NMR: 2.5 (t), 3.5 (t), 13.9 (q), 16.4 (d), 19.8 (q), 20.8
(t), 33.3 (t), 75.3 (d), 120.6 (d), 135.0 (d), 171.6 (s);
.sup.1H-NMR: 0.20-0.26 (m, 1H); 0.35-0.40 (m, 1H); 0.45-0.56 (m,
2H); 0.94-1.03 (m, 1H); 0.98 (t, J=7.5, 3H); 1.29 (d, J=6.4, 3H);
2.03-2.11 (m, 2H); 3.07 (d, J=6.7, 2H); 4.31-4.38 (m, 1H);
5.50-5.61 (m, 2H).
Cyclopropylmethyl Hexanoate
Prepared from hexanoic acid and cyclopropanemethanol according to
the ester preparation method A described above.
Bp.: 65.degree. C./6 mbar
.sup.13C NMR: 3.2 (t), 9.9 (d), 13.9 (q), 22.4 (t), 24.8 (t), 31.4
(t), 34.4 (t), 69.0 (t), 174.0 (s);
.sup.1H-NMR: 0.25-0.29 (m, 2H); 0.53-0.58 (m, 2H); 0.90 (t, J=7.1,
3H); 1.07-1.17 (m, 1H); 1.28-1.36 (m, 4H); 1.61-1.68 (m, 2H); 2.31
(t, J=7.7, 2H); 3.90 (d, J=7.3, 2H).
(E)-cyclopropylmethyl hex-4-enoate
Prepared from (E)-methyl hex-4-enoate and cyclopropanemethanol
according to the ester preparation method B described above.
Bp.: 60-65.degree. C./2 mbar
.sup.13C NMR: 3.2 (t), 9.8 (d), 17.9 (q), 28.0 (t), 34.4 (t), 69.1
(t), 126.1 (d), 129.3 (d), 173.4 (s);
.sup.1H-NMR: 0.25-0.29 (m, 2H); 0.53-0.58 (m, 2H); 1.07-1.17 (m,
1H); 1.64 (d, J=6.0 Hz, 3H); 2.28-2.40 (m, 4H); 3.90 (d, J=7.3,
2H); 5.39-5.53 (m, 2H).
Cyclopropylmethyl Heptanoate
Prepared from allyl heptanoate and cyclopropanemethanol according
to the ester preparation method C described above.
Bp.: 71.degree. C./2 mbar
.sup.13C NMR: 3.2 (t), 9.9 (d), 14.0 (q), 22.5 (t), 25.0 (t), 28.9
(t), 31.5 (t), 34.4 (t), 69.0 (t), 174.0 (s);
.sup.1H-NMR: 0.25-0.29 (m, 2H); 0.53-0.58 (m, 2H); 0.89 (t, J=7.1,
3H); 1.07-1.17 (m, 1H); 1.25-1.37 (m, 6H), 1.60-1.67 (m, 2H); 2.31
(t, J=7.6, 2H); 3.90 (d, J=7.3, 2H).
Cyclopropylmethyl 3-cyclohexylpropanoate
Prepared from allyl 3-cyclohexylpropanoate and cyclopropanemethanol
according to the ester preparation method C described above.
Bp.: 66.degree. C./0.1 mbar
.sup.13C NMR: 3.2 (t), 9.9 (d), 26.3 (t), 26.6 (t), 32.0 (t), 32.4
(t), 33.0 (t), 37.3 (d), 69.0 (t), 174.3 (s);
.sup.1H-NMR: 0.25-0.29 (m, 2H); 0.53-0.58 (m, 2H); 0.84-0.95 (m,
2H); 1.07-1.30 (m, 5H); 1.51-1.57 (m, 2H); 1.62-1.73 (m, 5H); 2.33
(t, J=7.9, 2H); 3.90 (d, J=7.3, 2H).
Cyclopropylmethyl Octanoate
Prepared from allyl octanoate and cyclopropanemethanol according to
the ester preparation method C described above.
Bp.: 76.degree. C./0.1 mbar
.sup.13C-NMR: 3.2 (t), 9.9 (d), 14.1 (q), 22.6 (t), 25.1 (t), 29.0
(t), 29.2 (t), 31.7 (t), 34.4 (t), 69.0 (t), 174.0 (s);
.sup.1H-NMR: 0.25-0.29 (m, 2H); 0.53-0.58 (m, 2H); 0.88 (t, J=7.0,
3H); 1.07-1.17 (m, 1H); 1.25-1.37 (m, 8H); 1.60-1.67 (m, 2H); 2.31
(t, J=7.5, 2H); 3.90 (d, J=7.3, 2H).
Cyclopropylmethyl 2-methylhexanoate
Prepared from 2-methylhexanoic acid and cyclopropanemethanol
according to the ester preparation method A described above.
Bp.: 65.degree. C./1 mbar
.sup.13C-NMR: 3.2 (t), 9.9 (d), 14.0 (q), 17.2 (q), 22.6 (t), 29.5
(t), 33.6 (t), 39.6 (d), 68.8 (t), 177.1 (s);
.sup.1H-NMR: 0.25-0.29 (m, 2H); 0.53-0.58 (m, 2H); 0.89 (t, J=7.0,
3H); 1.07-1.17 (m, 1H); 1.15 (d, J=7.0, 3H); 1.24-1.35 (m, 4H);
1.38-1.47 (m, 1H); 1.62-1.71 (m, 1H); 2.40-2.49 (m, 1H); 3.91 (d,
J=7.2, 2H).
(E)-1-cyclopropylethyl 2-methyl-2-hexenoate
Prepared from ethyl (E)-2-methyl-2-hexenoate and cyclopropyl methyl
carbinol according to the ester preparation method C described
above.
Bp.: 72.degree. C./2 mbar
.sup.13C-NMR: 2.4 (t), 3.5 (t), 12.4 (q), 14.0 (q), 16.4 (d), 19.9
(q), 21.9 (t), 30.8 (t), 74.8 (d), 128.3 (s), 141.9 (d), 167.9
(s);
.sup.1H-NMR: 0.22-0.28 (m, 1H); 0.37-0.43 (m, 1H); 0.46-0.56 (m,
2H); 0.95 (t, J=7.5, 3H); 0.98-1.06 (m, 1H); 1.32 (d, J=6.3, 3H);
1.44-1.53 (m, 2H); 1.83 (s, 3H); 2.12-2.18 (m, 2H); 4.38-4.45 (m,
1H); 6.75 (t, J=7.0, 1H).
Cyclopropylmethyl 2-(2-ethylcyclopropyl)acetate
Prepared from cyclopropylmethyl-3-hexenoate (70/30 Z/E mixture)
according to the cyclopropanation method described above.
Bp.: 55.degree. C./0.5 mbar
.sup.13C-NMR: 3.2 (t), 9.9 (d), 10.6 (t), 11.7 (d), 14.2 (q), 17.4
(d), 22.1 (t), 33.9 (t), 69.0 (t), 173.8 (s);
.sup.1H-NMR: 0.26-0.30 (m, 2H); 0.54-0.58 (m, 2H); 0.69-0.83 (m,
2H); 0.98 (t, J=7.3, 3H); 1.07-1.41 (m, 5H); 2.16-2.41 (m, 2H);
3.93 (d, J=7.2, 2H).
(Z)-cyclobutylmethyl hex-3-enoate
Prepared from (Z) methyl hex-3-enoate and cyclobutanemethanol
according to the ester preparation method B described above.
Bp.: 81.degree. C./3 mbar
.sup.13C-NMR: 13.9 (q), 18.4 (t), 20.8 (t), 24.8 (t), 33.0 (t),
34.2 (d), 68.4 (t), 120.4 (d), 135.0 (d), 172.2 (s);
.sup.1H-NMR: 0.98 (t, J=7.5, 3H); 1.72-2.10 (m, 8H); 2.56-2.67 (m,
1H); 3.08 (d, J=6.3, 2H); 4.06 (d, J=6.7, 2H); 5.49-5.60 (m,
2H).
Mixture of (Z)-cyclopropylmethyl 3-methylhept-2-enoate and
(E)-cyclopropylmethyl 3-methylhept-2-enoate
Prepared from ethyl 3-methyl-2-heptenoate and cyclopropyl methyl
carbinol according to the ester preparation method B described
above.
Purified by bulb to bulb distillation at 110.degree. C./1 mbar
Major Isomer (E; 80%):
.sup.13C NMR: 3.2 (t), 9.9 (d), 13.9 (q), 18.8 (q), 22.3 (t), 29.6
(t), 40.7 (t), 68.3 (t), 115.5 (d), 160.4 (s), 167.0 (s);
.sup.1H-NMR: 0.26-0.30 (m, 2H); 0.54-0.58 (m, 2H); 0.91 (t, J=7.2,
3H); 1.10-1.18 (m, 1H); 1.29-1.36 (m, 2H); 1.43-1.50 (m, 2H); 2.14
(t, J=7.9, 2H); 2.16 (s, 3H); 3.92 (d, J=7.2, 2H); 5.7 (s, 1H).
Minor Isomer (Z; 18%):
.sup.13C-NMR: 3.2 (t), 9.9 (d), 14.0 (q), 25.2 (t), 30.4 (t), 33.2
(t), 40.7 (t), 68.3 (t), 116.0 (d), 160.8 (s), 166.5 (s);
.sup.1H-NMR: 0.26-0.30 (m, 2H); 0.54-0.58 (m, 2H); 0.92 (t, J=7.2,
3H); 1.10-1.18 (m, 1H); 1.29-1.36 (m, 2H); 1.43-1.50 (m, 2H); 1.88
(s, 3H); 2.63 (t, J=7.8, 2H); 2.16 (s, 3H); 3.91 (d, J=7.2, 2H);
5.7 (s, 1H).
(Z)-(1-methylcyclopropyl)methyl hex-3-enoate
Prepared from (Z) methyl hex-3-enoate and
(1-methylcyclopropyl)methanol according to the ester preparation
method B described above.
Purified by bulb to bulb distillation at 85.degree. C./1 mbar
.sup.13C-NMR: 11.3 (t), 13.9 (q), 15.2 (s), 20.8 (t), 20.9 (q),
32.9 (t), 72.3 (t), 120.4 (d), 135.0 (d), 172.2 (s);
.sup.1H-NMR: 0.35-0.37 (m, 2H); 0.46-0.49 (m, 2H); 0.99 (t, J=7.6,
3H); 1.12 (s, 3H); 2.04-2.11 (m, 2H); 3.11 (d, J=5.9, 2H); 3.89 (s,
2H); 5.50-5.62 (m, 2H).
Example 2
Preparation of a Perfuming Composition
A shower gel's perfuming composition, of the gourmand, fruity,
musky type, was prepared by admixing the following ingredients:
TABLE-US-00002 Ingredient Parts by weight Benzyl acetate 350 Anisic
aldehyde 290 Hexylcinnamic aldehyde 450 10%* Ethyl
2-methyl-pentanoate .sup.1) 50 Gamma undecalactone 150 Allyl
cyclohexylpropionate 10 Cis-2-pentyl-1-cyclopentanol .sup.1) 20
(1'R,E)-2-ethyl-4-(2',2',3'-trimethyl-3'- 50
cyclopenten-1'-yl)-2-buten-1-ol .sup.1) Ethylpraline 35
Ethylvanilline 60 1,3-Benzodioxole-5-carbaldehyde .sup.1) 100
Helvetolide .RTM. .sup.2) 500 Melonal .RTM. .sup.3) 5 Lilly of the
valley composition .sup.1) 20 Hedione .RTM. .sup.4) 50
Octanolide-1,4 270 Orange essential oil 100 Hexyl salicylate 380
Vertofix Coeur .RTM. .sup.5) 90 2980 *in dipropyleneglycol .sup.1)
origin: Firmenich SA, Geneva, Switzerland .sup.2)
(1S,1'R)-2-[1-(3',3'-dimethyl-1'-cyclohexyl)ethoxy]-2-methylpropy-
l propanoate; origin: Firmenich SA, Geneva, Switzerland .sup.3)
2,6-dimethyl-5-heptanal; origin: Givaudan-Roure SA, Vernier,
Switzerland .sup.4) methyl dihydrojasmonate; origin: Firmenich SA,
Geneva, Switzerland .sup.5) methyl cedryl ketone; origin:
International Flavors & Fragrances, USA
The addition of 20 parts by weight of cyclopropylmethyl
(3Z)-3-hexenoate to the above-described composition clearly
imparted to the latter a fresh sparkling tonality reminding of a
juicy green pear. This effect was not obtained with the addition of
other derivatives of cis-3-hexenol which are known ingredients
imparting green notes.
Example 3
Preparation of a Perfuming Composition
A perfuming composition, of the linden type, was prepared by
admixing the following ingredients:
TABLE-US-00003 Ingredient Parts by weight Benzyl acetate 55 Dodecyl
acetate 270 Hydratropyl alcool 205 Anisic aldehyde 20 Cuminic
aldehyde 2 Dihydro Eugenol 20 1,3-Benzodioxole-5-carbaldehyde
.sup.1) 15 Hivernal .RTM. .sup.2) 10 Isoeugenol 5 Mayol .RTM.
.sup.3) 275 Methylacetophenone 5
(1'R)-2-[2-(4'-methyl-3'-cyclohexen- 3 1'-yl)propyl] Cyclopentanone
.sup.1) 10%* Neobutenone .RTM. Alpha .sup.4) 5 Methyl Octin
carbonate 5 1%* Nonadienal 5 Phenethylol 30 Methyl salicylate 5
Terpineol 20 Undecavertol .RTM. .sup.5) 5 Ionone Alpha 20 10%**
Violettyne .sup.6) 15 995 *in dipropyleneglycol **in isopropyle
myristate .sup.1) origin: Firmenich SA, Geneva, Switzerland .sup.2)
3-(3,3-dimethyl-5-indanyl)propanal; origin: Firmenich SA, Geneva,
Switzerland .sup.3) cis-7-P-menthanol; origin: Firmenich SA,
Geneva, Switzerland .sup.4)
1-(5,5-dimethyl-1-cyclohexen-1-yl)-4-penten-1-one; origin:
Firmenich SA, Geneva, Switzerland .sup.5) 4-methyl-3-decen-5-ol;
origin: Givaudan-Roure SA, Vernier, Switzerland .sup.6)
1,3-undecadien-5-yne; origin: Firmenich SA, Geneva, Switzerland
The addition of 5 parts by weight of cyclopropylmethyl
(3Z)-3-hexenoate to the above-described linden composition imparted
to the latter a much more natural and sparkling connotation
reinforcing the violet leaf aspects (provided by Methyl Octin
carbonate, nonadienal, undecavertol and violettyne), as well as
conferring a nice green, pear connotation.
When instead of the invention's compound there was added a
derivatives of cis-3-hexenol, known to imparting green notes, the
total effect was much less powerful and rising and also definitely
devoid of the green, pear connotation.
* * * * *